US4103002A - Bioglass coated A1203 ceramics - Google Patents

Bioglass coated A1203 ceramics Download PDF

Info

Publication number
US4103002A
US4103002A US05/766,749 US76674977A US4103002A US 4103002 A US4103002 A US 4103002A US 76674977 A US76674977 A US 76674977A US 4103002 A US4103002 A US 4103002A
Authority
US
United States
Prior art keywords
glass
biologically active
ceramic
ceramic surface
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/766,749
Inventor
Larry Leroy Hench
David Charles Greenspan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Florida
Original Assignee
University of Florida
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Florida filed Critical University of Florida
Priority to US05/766,749 priority Critical patent/US4103002A/en
Application granted granted Critical
Publication of US4103002A publication Critical patent/US4103002A/en
Assigned to UNIVERSITY OF FLORIDA, reassignment UNIVERSITY OF FLORIDA, ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BOARD OF REGENTS, STATE OF FLORIDA
Assigned to REBUILDING SERVICES INC., WASHINGTON RESOURCES GROUP, INC., GRYPHON VENTURES, LIMITED PARTERSHIP, VENTURE FIRST II L.P. reassignment REBUILDING SERVICES INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GELTECH INC., A CORP. OF DE
Assigned to REBUILDING SERVICE, INC., KNELLINGER, RICHARD M., GRYPHON VENTURES I, LIMITED PARTNERSHIP, VENTURE FIRST II L.P., WASHINGTON RESOURCES GROUP, INC., HENCH, LARRY reassignment REBUILDING SERVICE, INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GELTECH, INC., A CORPORATION OF DE
Assigned to WASHINGTON RESOURCES GROUP, INC., GRYPHON VENTURES II, LIMITED PARTNERSHIP, REBUILDING SERVICE, INC., VENTURE FIRST II L.P. reassignment WASHINGTON RESOURCES GROUP, INC. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GELTECH, INC.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/28—Bones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2002/30001—Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
    • A61F2002/30003—Material related properties of the prosthesis or of a coating on the prosthesis
    • A61F2002/30004—Material related properties of the prosthesis or of a coating on the prosthesis the prosthesis being made from materials having different values of a given property at different locations within the same prosthesis
    • A61F2002/30037—Material related properties of the prosthesis or of a coating on the prosthesis the prosthesis being made from materials having different values of a given property at different locations within the same prosthesis differing in coefficient of thermal expansion or dila(ta)tion
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A61F2002/30929—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth having at least two superposed coatings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00179—Ceramics or ceramic-like structures
    • A61F2310/00185—Ceramics or ceramic-like structures based on metal oxides
    • A61F2310/00203—Ceramics or ceramic-like structures based on metal oxides containing alumina or aluminium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00928—Coating or prosthesis-covering structure made of glass or of glass-containing compounds, e.g. of bioglass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24471—Crackled, crazed or slit

Definitions

  • Al 2 O 3 ceramics make them ideal for use in the construction of artificial protheses and orthopedic devices.
  • the biological inactivity of Al 2 O 3 ceramic surfaces makes it extremely difficult, if not impossible, to achieve cement-free implantation of the prothesis since bone tissue will not bond or grow thereon.
  • the present invention comprises a method of coating a compacted Al 2 O 3 ceramic surface with a biologically active glass having a thermal coefficient of expansion different from that of the ceramic comprising:
  • the invention also relates to the product of the above-described process.
  • the biologically active glass coated compacted Al 2 O 3 ceramic of the present invention comprises a ceramic surface coated with at least two layers of biologically active glass having a thermal coefficient of expansion different from that of the Al 2 O 3 ceramic wherein the first layer is bonded to the ceramic surface by ion diffusion and is characterized by having interconnected thermo-mechanical stress induced micro-cracks therein and wherein the subsequent layer or layers are coated thereover.
  • the invention also relates to a cement-free bone prothesis implant comprising the above-described bioactive glass coated Al 2 O 3 ceramic.
  • thermo-mechanical stresses in the biologically active glass glaze coating are relied upon to induce thermo-mechanical stresses in the biologically active glass glaze coating.
  • the glaze cracks in order to relieve the stresses due to thermal mismatch, thereby resulting in isolated islands of biologically active glass coating separated by small interconnected flaws or micro-cracks. These cracks range from about 0.05 to 0.8 microns wide.
  • the small islands of biologically active glass are bonded to the compacted Al 2 O 3 ceramic surface by a large diffusional bond which is developed by processing at elevated temperatures (1100°-1350° C.).
  • the diffusional bond is a chemical bond between the Al 2 O 3 substrate and the biologically active glass coating thereby eliminating a welldefined Al 2 O 3 -biologically active glass interface and results in an enhancement of the overall strength characteristics of the ceramic.
  • the resulting structure has the capacity to bond living tissues to an implant material comprised of the coated ceramic substrate due to the properties of the biologically active glass.
  • the coating process does not deleteriously affect the mechanical strength of the Al 2 O 3 ceramic since all thermo-mechanical stresses are relieved during the first coating operation and no further stresses are induced by the second and subsequent glass coating steps.
  • the strength of the compacted Al 2 O 3 ceramic can actually be enhanced.
  • the strength and fatigue resistance of the Al 2 O 3 ceramic is increased.
  • any biologically active glass may be employed for the purposes of the present invention. It will be understood by those skilled in the art that any suitable biologically active glass, depending upon the ultimate use for which the coated ceramic is intended, may be utilized. Generally, the biologically active glass is one capable of bonding to living tissue and contains, by weight:
  • Na 2 O + CaO must be above 30% to achieve bonding to live tissue.
  • Suitable specific glasses include those of the following compositions:
  • a compacted Al 2 O 3 ceramic having a thermal coefficient of expansion (0°-1,000° C.) in the range 35-75 ⁇ 10 -7 in/in/° C. and a biologically active glass having a thermal coefficient of expansion (0°-1,000° C.) in the range 95-145 ⁇ 10 -7 in/in/° C.
  • the biologically active glasses are first melted (e.g., in platinum crucibles) for 3-12 hours to insure homogeneity.
  • the melting temperatures range from about 1300° C. to about 1550° C.
  • the biologically active glass is quenched in water and ground in a ball mill into glass frit of the desired particle size. Generally, a particle size of less than about 74 microns is preferred.
  • the frit is then mixed with an organic binder (e.g., organic polymers such as a mixture of 20% polyvinylacetate and 80% polyvinylalcohol) and a suitable organic solvent (e.g., toluene, acetone, xylene, etc.) to form a slurry.
  • organic binder e.g., organic polymers such as a mixture of 20% polyvinylacetate and 80% polyvinylalcohol
  • a suitable organic solvent e.g., toluene, acetone, xylene, etc.
  • the amount of binder used depends upon the particle size of the frit employed. Generally, larger particles require greater amounts of binder to achieve adequate coverage.
  • the amount of solvent employed is varied to control the viscosity of the slurry and the thickness of the ultimate coating. Generally, the slurry will contain from about 35 to about 80 percent glass frit, from about 1 to about 10 percent binder, and from about 20 to about 65 percent organic solvent, all percentages being by weight.
  • the compacted Al 2 O 3 substrate to be coated is then dipped into the slurry or the slurry is handpainted or sprayed onto the substrate. The coating is allowed to dry thoroughly.
  • the coated substrate is then fired following a schedule that will allow burn-off of the organic binder, followed by a softening of the glass and subsequent bonding of the glass to the substrate by ion diffusion.
  • the high alkali content of the biologically active glass is one of the major factors that allows for good diffusional bonding between the coating and the substrate.
  • the coated glass is then annealed to relieve mechanical stresses.
  • FIG. 1 sets forth a double coated structure, it will be understood by those skilled in the art that successive coats of biologically active glass may be applied thereover following the same firing schedule, depending upon the desired surface properties of the resulting coated system.
  • the biologically active glass glaze ultimately coated upon the compacted Al 2 O 3 ceramic surface contains 0.475 moles of Na 2 O,0.525 moles CaO, 0.050 moles P 2 O 5 , and 0.900 moles SiO 2 (normalized with respect to alkali content).
  • composition of the glasses which allows for relatively high diffusion rates and (2) the various time-temperature firing schedules which control the amount of diffusion permit the controlled micro-cracking of the base coat of biologically active glass.
  • the control of these two variables also permits regulation of the diffusion bonding which is ultimately responsible for the success of the coated system.
  • the temperature to which the coated system is subjected to achieve ion diffusion bonding depends, of course, on the particular glass and Al 2 O 3 ceramic compositions employed. Generally, temperatures above 500° C., preferably in the range of 900° to 1400° C., and most preferably from 1100° to 1350° C., are utilized.
  • the first coat is applied such that the ultimate thickness thereof is from about 25-100 microns. Subsequent coatings may range from about 50 to about 400 microns.
  • FIG. 2 sets forth an electron micro probe scan of sodium and aluminum in the single coated structure set forth above.
  • the degree of diffusional bonding is apparent from the fact that alumina is found as far into the glass as 200 microns.
  • FIG. 3 sets forth an electron micro probe scan of sodium and aluminum in the above-described double coated system. The fact that the second coating is largely bonded to the first glass coating is apparent from the decreased intensity of the alumina signal in the second layer of the glass coating.
  • FIG. 4 sets forth the strain rate dependence of the biologically active glass coated vs. uncoated Al 2 O 3 surface. It is apparent that the fatigue resistance of the coated material is greater as compared with the uncoated substrate.
  • ⁇ gl 100 ⁇ 10 -7 in/in/° C.
  • ⁇ b 50 ⁇ 10 -7 in/in/° C.
  • the thermal stress is found to be 8.2 ⁇ 10 -3 psi. It is, therefore, apparent that the degree of micro cracking can be calculated, depending upon the particular compositions employed and the firing, coating and annealing schedules followed.
  • FIG. 5 sets forth the coated ceramic substrate in various stages of formation.
  • the ceramic substrate 1 is overcoated with the first layer of biologically active glass 2.
  • micro-cracks 3 appear in the coating 2 forming islands 4 of biologically active glass bonded, by ion diffusion, to the ceramic substrate 1.
  • FIG. 5c depicts a micro-cracked biologically active glass coated Al 2 O 3 ceramic substrate overcoated with a second biologically active glass layer 5.
  • the thus coated Al 2 O 3 ceramic substrates are ideally adapted for the formation of cement-free bone prothesis implants of unusually high strength and capable of forming bonds with biologically active tissue.

Abstract

A method of coating a Al2 O3 ceramic surface with a biologically active glass comprising contacting a glass and ceramic having different thermal coefficients of expansion at a temperature sufficient to bond the glass to the ceramic surface by ion diffusion, cooling the coated substrate to a temperature sufficient to produce thermo-mechanical stress induced interconnected micro-cracks in the glass coating and overcoating said micro-cracked glass coating with at least one additional coating of biologically active glass. The invention includes a product of manufacture comprising a compacted Al2 O3 ceramic surface coated with at least two layers of biologically active glass characterized in that the first layer of glass has interconnected thermo-mechanical stress induced micro-cracks therein.

Description

BACKGROUND OF THE INVENTION
The strength, anti-friction and high wear resistance properties of Al2 O3 ceramics make them ideal for use in the construction of artificial protheses and orthopedic devices. The biological inactivity of Al2 O3 ceramic surfaces, however, makes it extremely difficult, if not impossible, to achieve cement-free implantation of the prothesis since bone tissue will not bond or grow thereon.
Various techniques have recently been suggested for activating the ceramic surfaces in order to enhance the bone-tissue bonding capabilities of the Al2 O3 prothesis. However, all of these techniques are either extremely expensive and time-consuming or result in ceramic structures of decreased mechanical strength, anti-friction properties and wear resistance.
It is an object of the present invention to provide a cement-free bone prothesis implant comprising a bioactive Al2 O3 ceramic and a method for the preparation thereof which is inexpensive and does not result in a decrease of the mechanical strength, anti-friction and wear resistance properties of the Al2 O3 ceramic material.
SUMMARY OF THE INVENTION
The present invention comprises a method of coating a compacted Al2 O3 ceramic surface with a biologically active glass having a thermal coefficient of expansion different from that of the ceramic comprising:
1. Contacting the glass with the ceramic surface at a temperature and for a time sufficient to bond the glass to the ceramic surface by ion diffusion,
2. Cooling the coated substrate to a temperature sufficient to produce interconnected micro-cracks in the glass coating as a result of the thermo-mechanical stresses induced by the differential in thermal coefficients of expansion of said ceramic and glass, and,
3. Overcoating the micro-cracked glass coating with at least one additional coating of the biologically active glass.
The invention also relates to the product of the above-described process.
The biologically active glass coated compacted Al2 O3 ceramic of the present invention comprises a ceramic surface coated with at least two layers of biologically active glass having a thermal coefficient of expansion different from that of the Al2 O3 ceramic wherein the first layer is bonded to the ceramic surface by ion diffusion and is characterized by having interconnected thermo-mechanical stress induced micro-cracks therein and wherein the subsequent layer or layers are coated thereover.
The invention also relates to a cement-free bone prothesis implant comprising the above-described bioactive glass coated Al2 O3 ceramic.
DETAILED DESCRIPTION OF THE INVENTION
It is well known that when applying a glaze of higher thermal expansion to a body of lower thermal expansion, thermal stresses will arise upon cooling. Since these thermal stresses result in an overall weakening of the coated structure, it is conventional according to prior art practices to attempt to match the thermal coefficients of expansion of the respective materials as closely as possible in order to minimize these stresses. This necessarily results in a drastic reduction in the number and variety of coatings which can be applied to a particular substrate.
According to the present invention, extreme mismatches between the relative thermal coefficients of expansion are relied upon to induce thermo-mechanical stresses in the biologically active glass glaze coating. Upon cooling, the glaze cracks in order to relieve the stresses due to thermal mismatch, thereby resulting in isolated islands of biologically active glass coating separated by small interconnected flaws or micro-cracks. These cracks range from about 0.05 to 0.8 microns wide. The small islands of biologically active glass are bonded to the compacted Al2 O3 ceramic surface by a large diffusional bond which is developed by processing at elevated temperatures (1100°-1350° C.). The diffusional bond is a chemical bond between the Al2 O3 substrate and the biologically active glass coating thereby eliminating a welldefined Al2 O3 -biologically active glass interface and results in an enhancement of the overall strength characteristics of the ceramic.
Multiple coatings of biologically active glass can then be applied over the micro-cracked glaze with no danger of inducing thermo-mechanical stresses in the structure. This is due to the fact that the second and subsequent glass layers are bonded to the first biologically active glass layer and not to the Al2 O3 substrate. Thus, the second glass layer has physical properties identical to the first glass layer with no mismatch in the respective coefficients of thermal expansion.
The resulting structure has the capacity to bond living tissues to an implant material comprised of the coated ceramic substrate due to the properties of the biologically active glass. In addition, the coating process does not deleteriously affect the mechanical strength of the Al2 O3 ceramic since all thermo-mechanical stresses are relieved during the first coating operation and no further stresses are induced by the second and subsequent glass coating steps.
Since no regard need be given to the thermal coefficient of expansion match, a wider variety of biologically active glass materials can be coated upon the ceramic surface than by the techniques presently prevalent in the prior art.
Indeed, by carefully controlling the coating procedure, the strength of the compacted Al2 O3 ceramic can actually be enhanced. By maintaining the size of the flaws or micro-cracks at below 1 micron, the strength and fatigue resistance of the Al2 O3 ceramic is increased.
Any biologically active glass may be employed for the purposes of the present invention. It will be understood by those skilled in the art that any suitable biologically active glass, depending upon the ultimate use for which the coated ceramic is intended, may be utilized. Generally, the biologically active glass is one capable of bonding to living tissue and contains, by weight:
SiO2 -- 40- 62%
Na2 O -- 10- 32%
CaO -- 10- 32%
P2 O5 -- 3- 9%
CaF2 -- 0- 18%
B2 O3 -- 0- 7.5%
Na2 O + CaO must be above 30% to achieve bonding to live tissue.
Suitable specific glasses include those of the following compositions:
A.
SiO2 -- 45.0%
Na2 O -- 24.5%
CaO -- 24.5%
P2 O5 -- 6.0%
B.
SiO2 -- 42.94%
Na2 O -- 23.37%
CaO -- 11.69%
P2 O5 -- 5.72%
CaF2 -- 16.26%
C.
SiO2 -- 40.0%
Na2 O -- 24.5%
CaO -- 24.5%
P2 O5 -- 6.0%
B2 O3 -- 5.0%
In order to achieve the micro-cracked glass coating, it is generally preferred to employ a compacted Al2 O3 ceramic having a thermal coefficient of expansion (0°-1,000° C.) in the range 35-75 × 10-7 in/in/° C. and a biologically active glass having a thermal coefficient of expansion (0°-1,000° C.) in the range 95-145 × 10-7 in/in/° C.
The biologically active glasses are first melted (e.g., in platinum crucibles) for 3-12 hours to insure homogeneity. The melting temperatures range from about 1300° C. to about 1550° C. After melting, the biologically active glass is quenched in water and ground in a ball mill into glass frit of the desired particle size. Generally, a particle size of less than about 74 microns is preferred. The frit is then mixed with an organic binder (e.g., organic polymers such as a mixture of 20% polyvinylacetate and 80% polyvinylalcohol) and a suitable organic solvent (e.g., toluene, acetone, xylene, etc.) to form a slurry. The amount of binder used depends upon the particle size of the frit employed. Generally, larger particles require greater amounts of binder to achieve adequate coverage. The amount of solvent employed is varied to control the viscosity of the slurry and the thickness of the ultimate coating. Generally, the slurry will contain from about 35 to about 80 percent glass frit, from about 1 to about 10 percent binder, and from about 20 to about 65 percent organic solvent, all percentages being by weight.
The compacted Al2 O3 substrate to be coated is then dipped into the slurry or the slurry is handpainted or sprayed onto the substrate. The coating is allowed to dry thoroughly.
The coated substrate is then fired following a schedule that will allow burn-off of the organic binder, followed by a softening of the glass and subsequent bonding of the glass to the substrate by ion diffusion. The high alkali content of the biologically active glass is one of the major factors that allows for good diffusional bonding between the coating and the substrate. The coated glass is then annealed to relieve mechanical stresses.
Employing the biologically active glass composition A described above and a compacted Al2 O3 ceramic having a thermal coefficient of expansion of 50-75 × 10-7 in/in° C., the firing schedule set forth in FIG. 1 was employed. Although FIG. 1 sets forth a double coated structure, it will be understood by those skilled in the art that successive coats of biologically active glass may be applied thereover following the same firing schedule, depending upon the desired surface properties of the resulting coated system. The biologically active glass glaze ultimately coated upon the compacted Al2 O3 ceramic surface contains 0.475 moles of Na2 O,0.525 moles CaO, 0.050 moles P2 O5, and 0.900 moles SiO2 (normalized with respect to alkali content).
The combination of (1) composition of the glasses (high alkali, low silica) which allows for relatively high diffusion rates and (2) the various time-temperature firing schedules which control the amount of diffusion permit the controlled micro-cracking of the base coat of biologically active glass. The control of these two variables also permits regulation of the diffusion bonding which is ultimately responsible for the success of the coated system.
The temperature to which the coated system is subjected to achieve ion diffusion bonding depends, of course, on the particular glass and Al2 O3 ceramic compositions employed. Generally, temperatures above 500° C., preferably in the range of 900° to 1400° C., and most preferably from 1100° to 1350° C., are utilized.
The first coat is applied such that the ultimate thickness thereof is from about 25-100 microns. Subsequent coatings may range from about 50 to about 400 microns.
FIG. 2 sets forth an electron micro probe scan of sodium and aluminum in the single coated structure set forth above. The degree of diffusional bonding is apparent from the fact that alumina is found as far into the glass as 200 microns.
FIG. 3 sets forth an electron micro probe scan of sodium and aluminum in the above-described double coated system. The fact that the second coating is largely bonded to the first glass coating is apparent from the decreased intensity of the alumina signal in the second layer of the glass coating.
FIG. 4 sets forth the strain rate dependence of the biologically active glass coated vs. uncoated Al2 O3 surface. It is apparent that the fatigue resistance of the coated material is greater as compared with the uncoated substrate.
As noted above, the application of a glaze of higher thermal expansion on a body of lower thermal expansion will result in thermal stresses upon cooling. These stresses can be calculated employing the following equation:
σgl = E(T.sub.o - T') (αgl - α.sub.b) (1 - 3j + 6j.sup.2)
where
j = glaze thickness/body thickness
αgl = thermal expansion of glaze
E = youngs modulus
αb = thermal expansion of body
To = annealing temperature of glaze
σg' = thermal stress (psi)
T = final temperature [room temp. (20° C.)]
In the above-described example employing composition A:
j = 0.02
T° = 450° c.
e = 8 × 106
t' = 20° c.
αgl = 100 × 10-7 in/in/° C.
αb = 50 × 10-7 in/in/° C.
Substituting these parameters into the above equation, the thermal stress is found to be 8.2 × 10-3 psi. It is, therefore, apparent that the degree of micro cracking can be calculated, depending upon the particular compositions employed and the firing, coating and annealing schedules followed.
FIG. 5 sets forth the coated ceramic substrate in various stages of formation.
In FIG. 5a, wherein the temperature is greater than 500° C., the ceramic substrate 1 is overcoated with the first layer of biologically active glass 2.
In FIG. 5b, wherein the system has been cooled to room temperature, micro-cracks 3 appear in the coating 2 forming islands 4 of biologically active glass bonded, by ion diffusion, to the ceramic substrate 1.
FIG. 5c depicts a micro-cracked biologically active glass coated Al2 O3 ceramic substrate overcoated with a second biologically active glass layer 5.
The thus coated Al2 O3 ceramic substrates are ideally adapted for the formation of cement-free bone prothesis implants of unusually high strength and capable of forming bonds with biologically active tissue.

Claims (20)

What is claimed is:
1. A method of coating a compacted Al2 O3 ceramic surface with a biologically active glass, said ceramic and glass having different thermal coefficients of expansion, comprising:
(1) contacting said glass with said ceramic surface at a temperature and for a time sufficient to bond said glass to said ceramic surface by ion diffusion,
(2) cooling said coated substrate to a temperature sufficient to produce interconnected micro-cracks in said glass coating as a result of the thermo-mechanical stresses induced by the differential in thermal coefficients of expansion of said ceramic and glass, and
(3) overcoating said micro-cracked glass coating with at least one additional coating of biologically active glass.
2. The method of claim 1 wherein said biologically active glass contains, by weight:
SiO2 -- 40-62%
Na2 O -- 10-32%
CaO -- 10-32%
P2 o5 -- 3-9%
caF2 -- 0-18%
B2 o3 -- 0-7.5%
3. the method of claim 1 wherein said biologically active glass contains, by weight:
SiO2 -- 45.0%
Na2 O -- 24.5%
CaO -- 24.5%
P2 o5 -- 6.0%
4. the method of claim 1 wherein said biologically active glass contains, by weight:
SiO2 -- 42.94%
Na2 O -- 23.37%
CaO -- 11.69%
P2 o5 -- 5.72%
caF2 -- 16.26%
5. The method of claim 1 wherein said biologically active glass contains, by weight:
SiO2 -- 40.0%
Na2 O -- 24.5%
CaO -- 24.5%
P2 o5 -- 6.0%
b2 o3 -- 5.0%
6. the method of claim 1 wherein said ceramic surface has a thermal coefficient of expansion (0°-1,000° C.) in the range 50-75 × 10-7 in/in/° C. and said glass has a thermal coefficient of expansion (0°-1,000° C.) in the range 95-145 × 10-7 in/in/° C.
7. The method of claim 1 wherein each of said coatings is annealed.
8. The method of claim 1 wherein said glass is bonded to said ceramic surface at a temperature above 500° C.
9. The method of claim 1 wherein said glass coated ceramic surface is cooled so as to produce micro-cracks in said glass coating having a width less than 1 μm.
10. The product of the process of claim 1.
11. A cement-free bone prothesis implant comprising the product of the process of claim 1.
12. The method of claim 1 wherein said glass is contacted with said ceramic surface by coating said ceramic surface with a slurry comprising a solvent, an orgnic binder, and a biologically active glass frit having a particle size less than 74 μm.
13. The method of claim 12 including the steps of drying the slurry coated ceramic substrate and firing the coated substrate to burn off said organic binder.
14. A product of manufacture comprising a compacted Al2 O3 ceramic surface coated with at least two layers of biologically active glass having a thermal coefficient of expansion different from that of said Al2 O3 ceramic, said first layer being bonded to said ceramic surface through ion-diffusion and characterized by having interconnected thermo-mechanical stress induced micro-cracks therein, and said subsequent layer or layers being successively bonded thereover.
15. The product of claim 14 wherein said biologically active glass contains, by weight:
SiO2 -- 40 - 62%
Na2 O -- 10 - 32%
CaO -- 10 - 32%
P2 o5 -- 3 - 9%
caF2 -- 0 - 18%
B2 o3 -- 0 - 7.5%
16. the product of claim 14 wherein said biologically active glass contains, by weight:
SiO2 -- 45.0%
Na2 O -- 24.5%
CaO -- 24.5%
P2 o5 -- 6.0%
17. the product of claim 14 wherein said bilogically active contains, by weight:
SiO2 -- 42.94%
Na2 O -- 23.37%
CaO -- 11.69%
P2 o5 -- 5.72%
caF2 -- 16.26%
18. The product of claim 14 wherein said bilogically active glass contains, by weight:
SiO2 -- 40.0%
Na2 O -- 24.5%
CaO -- 24.5%
P2 o5 -- 6.0%
b2 o3 -- 5.0%
19. the product of claim 14 wherein said ceramic surface has a thermal coefficient of expansion (0°-1,000° C.) in the range 50-75 × 10-7 in/in/° C. and said glass has a thermal coefficient of expansion (0°-1,000° C.) in the range 95-145 × 10-7 in/in/° C.
20. A cement-free bone prothesis implant comprising the product of claim 14.
US05/766,749 1977-02-08 1977-02-08 Bioglass coated A1203 ceramics Expired - Lifetime US4103002A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/766,749 US4103002A (en) 1977-02-08 1977-02-08 Bioglass coated A1203 ceramics

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/766,749 US4103002A (en) 1977-02-08 1977-02-08 Bioglass coated A1203 ceramics

Publications (1)

Publication Number Publication Date
US4103002A true US4103002A (en) 1978-07-25

Family

ID=25077413

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/766,749 Expired - Lifetime US4103002A (en) 1977-02-08 1977-02-08 Bioglass coated A1203 ceramics

Country Status (1)

Country Link
US (1) US4103002A (en)

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4234972A (en) * 1978-06-21 1980-11-25 Board Of Regents, State Of Florida Bioglass coated metal substrate
US4437192A (en) 1980-06-11 1984-03-20 Nippon Kogaku K.K. Implants of biologically active glass or glass ceramic containing titania
US4457948A (en) * 1982-07-26 1984-07-03 United Technologies Corporation Quench-cracked ceramic thermal barrier coatings
JPS60137849A (en) * 1983-10-27 1985-07-22 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− Carrier particle coated with biologically active glassy precursor
DE3526335A1 (en) * 1984-07-23 1986-01-30 Kyocera Corp., Kyoto CERAMIC PROSTHESIS
US4708652A (en) * 1984-03-06 1987-11-24 Nippon Kogaku K. K. Apatite composite ceramics
US4737411A (en) * 1986-11-25 1988-04-12 University Of Dayton Controlled pore size ceramics particularly for orthopaedic and dental applications
US4775646A (en) * 1984-04-27 1988-10-04 University Of Florida Fluoride-containing Bioglass™ compositions
US4786555A (en) * 1983-10-27 1988-11-22 E. I. Du Pont De Nemours And Company Support particles coated with or particles of precursors for or of biologically active glass
DE4020598A1 (en) * 1989-06-30 1991-01-03 Kyocera Corp Inorganic implant prosthesis - has ceramic substrate coated with glass interlayer and thermally sprayed calcium phosphate based outer layer
DE4006379A1 (en) * 1989-03-03 1991-04-18 Univ Schiller Jena Prodn. of implant with metal core
DE4113021A1 (en) * 1991-04-20 1992-10-22 Carus Carl Gustav Reabsorbing phosphate glass and ceramics bio material - contg. phosphorous pent-, calcium-, magnesium-, sodium- and potassium oxide(s) for tissue and bone replacement
EP0559508A1 (en) * 1992-03-06 1993-09-08 Zimmer S.A. Novel coating for prosthesis
WO1998011853A1 (en) * 1996-09-19 1998-03-26 Usbiomaterials Corporation Composition and method for acceleration of wound and burn healing
US5840290A (en) * 1996-05-30 1998-11-24 University Of Florida Research Foundation Injectable bio-active glass in a dextran suspension
US5972384A (en) * 1997-10-01 1999-10-26 University Of Maryland, Baltimore Use of biologically active glass as a drug delivery system
US5977204A (en) * 1997-04-11 1999-11-02 Osteobiologics, Inc. Biodegradable implant material comprising bioactive ceramic
US5981412A (en) * 1996-05-01 1999-11-09 University Of Florida Research Foundation Bioactive ceramics and method of preparing bioactive ceramics
US6051247A (en) * 1996-05-30 2000-04-18 University Of Florida Research Foundation, Inc. Moldable bioactive compositions
US6423343B1 (en) 1998-01-23 2002-07-23 Usbiomaterials Corporation Bioactive glass treatment of inflammation in skin conditions
US20020120033A1 (en) * 2000-08-11 2002-08-29 Weitao Jia Dental/medical compositions comprising degradable polymers and methods of manufacture thereof
US6482444B1 (en) 1999-06-14 2002-11-19 Imperial College Innovations Silver-containing, sol/gel derived bioglass compositions
WO2002098474A1 (en) 2001-06-05 2002-12-12 Laisheng Biotechnology Inc., Shanghai Scaffold product for human bone tissue engineering, methods for its preparation ans uses thereof
US6517863B1 (en) 1999-01-20 2003-02-11 Usbiomaterials Corporation Compositions and methods for treating nails and adjacent tissues
US6663878B1 (en) 1999-04-29 2003-12-16 Usbiomaterials Corp. Anti-inflammatory bioactive glass particulates
US20040086661A1 (en) * 2001-03-16 2004-05-06 Antti Yli-Urpo Sintering of bioactive glass with localised electromagnetic and/or acoustic energy
US6756060B1 (en) 1996-09-19 2004-06-29 Usbiomaterials Corp. Anti-inflammatory and antimicrobial uses for bioactive glass compositions
US20040226478A1 (en) * 2001-01-04 2004-11-18 Primus Carolyn M. Dental material
US20050022698A1 (en) * 2000-09-20 2005-02-03 Mazany Anthony M. Inorganic matrix compositions and composites incorporating the matrix composition
US20050240281A1 (en) * 1997-05-30 2005-10-27 Slivka Michael A Fiber-reinforced, porous, biodegradable implant device
DE102004021729A1 (en) * 2004-04-30 2005-11-24 Mann + Hummel Gmbh Hollow fiber membrane module
US20070129810A1 (en) * 2003-08-22 2007-06-07 Smith & Nephew, Inc. Tissue Repair and Replacement
US20070275021A1 (en) * 1999-12-07 2007-11-29 Schott Ag New cosmetic, personal care, cleaning agent, and nutritional supplement compositions and methods of making and using same
US20080221701A1 (en) * 2007-03-09 2008-09-11 Jipin Zhong Osteostimulative settable bone graft putty
US20090208428A1 (en) * 2006-06-16 2009-08-20 Imperial Innovations Limited Bioactive Glass
US7722246B1 (en) * 2005-04-20 2010-05-25 Carty William M Method for determining the thermal expansion coefficient of ceramic bodies and glazes
US20100203482A1 (en) * 2009-02-06 2010-08-12 The Trustees Of The University Of Pennsylvania Non-biodegradable endodontic sealant composition
US20100310515A1 (en) * 2007-12-17 2010-12-09 Queen Mary & Westfield College Latency Associated Protein Construct With Aggrecanase Sensitive Cleavage Site
US20110009511A1 (en) * 2007-07-05 2011-01-13 Imperial Innovations Limited Glass Polycarboxylate Cements
US20110123592A1 (en) * 2008-05-27 2011-05-26 Imperial Innovations Limited Biomaterials
US20110142902A1 (en) * 2008-05-27 2011-06-16 Imperial Innovations Limited Hypoxia Inducing Factor (HIF) Stabilising Glasses
US20120064290A1 (en) * 2008-12-01 2012-03-15 The Furlong Research Charitable Foundation Article and method of surface treatment of an article
US8795691B2 (en) 2010-03-16 2014-08-05 Brown University Nanotubes and compositions thereof
US9198842B2 (en) 2009-06-30 2015-12-01 Repregen Limited Multicomponent glasses for use in personal care products
WO2016090359A2 (en) 2014-12-05 2016-06-09 Augusta University Research Institute, Inc. Glass composites for tissue augmentation, biomedical and cosmetic applications
US9439766B2 (en) 2012-04-23 2016-09-13 Zimmer, Inc. Multi-layered prosthetic constructs, kits, and methods
US11464740B2 (en) 2019-04-29 2022-10-11 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Method and devices for delivering therapeutics by oral, respiratory, mucosal, transdermal routes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2866720A (en) * 1955-10-24 1958-12-30 American Marietta Co Decorative coating and method of making same
US3900630A (en) * 1972-12-29 1975-08-19 Dainippon Toryo Kk Decorative article having inorganic coating film having rugged pattern including cracks and process for production thereof
US3934961A (en) * 1970-10-29 1976-01-27 Canon Kabushiki Kaisha Three layer anti-reflection film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2866720A (en) * 1955-10-24 1958-12-30 American Marietta Co Decorative coating and method of making same
US3934961A (en) * 1970-10-29 1976-01-27 Canon Kabushiki Kaisha Three layer anti-reflection film
US3900630A (en) * 1972-12-29 1975-08-19 Dainippon Toryo Kk Decorative article having inorganic coating film having rugged pattern including cracks and process for production thereof

Cited By (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4234972A (en) * 1978-06-21 1980-11-25 Board Of Regents, State Of Florida Bioglass coated metal substrate
US4437192A (en) 1980-06-11 1984-03-20 Nippon Kogaku K.K. Implants of biologically active glass or glass ceramic containing titania
US4457948A (en) * 1982-07-26 1984-07-03 United Technologies Corporation Quench-cracked ceramic thermal barrier coatings
US4786555A (en) * 1983-10-27 1988-11-22 E. I. Du Pont De Nemours And Company Support particles coated with or particles of precursors for or of biologically active glass
JPS60137849A (en) * 1983-10-27 1985-07-22 イ−・アイ・デユポン・デ・ニモアス・アンド・カンパニ− Carrier particle coated with biologically active glassy precursor
US4608350A (en) * 1983-10-27 1986-08-26 E. I. Du Pont De Nemours And Company Precursor solutions for biologically active glass
AU574109B2 (en) * 1983-10-27 1988-06-30 E.I. Du Pont De Nemours And Company Bioglass
US4708652A (en) * 1984-03-06 1987-11-24 Nippon Kogaku K. K. Apatite composite ceramics
US4775646A (en) * 1984-04-27 1988-10-04 University Of Florida Fluoride-containing Bioglass™ compositions
US4878914A (en) * 1984-07-23 1989-11-07 Kyocera Corporation Ceramic prosthesis for living body & method of making the same
DE3526335A1 (en) * 1984-07-23 1986-01-30 Kyocera Corp., Kyoto CERAMIC PROSTHESIS
US4737411A (en) * 1986-11-25 1988-04-12 University Of Dayton Controlled pore size ceramics particularly for orthopaedic and dental applications
DE4006379C2 (en) * 1989-03-03 1999-06-10 Univ Schiller Jena Process for the production of bioactive and mechanically highly resilient implants
DE4006379A1 (en) * 1989-03-03 1991-04-18 Univ Schiller Jena Prodn. of implant with metal core
DE4020598A1 (en) * 1989-06-30 1991-01-03 Kyocera Corp Inorganic implant prosthesis - has ceramic substrate coated with glass interlayer and thermally sprayed calcium phosphate based outer layer
DE4113021A1 (en) * 1991-04-20 1992-10-22 Carus Carl Gustav Reabsorbing phosphate glass and ceramics bio material - contg. phosphorous pent-, calcium-, magnesium-, sodium- and potassium oxide(s) for tissue and bone replacement
EP0559508A1 (en) * 1992-03-06 1993-09-08 Zimmer S.A. Novel coating for prosthesis
FR2688139A1 (en) * 1992-03-06 1993-09-10 Zimmer Sa NEW COATING FOR PROTHETIC SYSTEM.
US5543209A (en) * 1992-03-06 1996-08-06 Zimmer, Inc. Surface coating for prosthesis system containing HA/TCP composition
US5981412A (en) * 1996-05-01 1999-11-09 University Of Florida Research Foundation Bioactive ceramics and method of preparing bioactive ceramics
US5840290A (en) * 1996-05-30 1998-11-24 University Of Florida Research Foundation Injectable bio-active glass in a dextran suspension
US6051247A (en) * 1996-05-30 2000-04-18 University Of Florida Research Foundation, Inc. Moldable bioactive compositions
US6428800B2 (en) 1996-09-19 2002-08-06 Usbiomaterials Corporation Composition and method for acceleration of wound and burn healing
WO1998011853A1 (en) * 1996-09-19 1998-03-26 Usbiomaterials Corporation Composition and method for acceleration of wound and burn healing
US5834008A (en) * 1996-09-19 1998-11-10 U.S. Biomaterials Corp. Composition and method for acceleration of wound and burn healing
US6756060B1 (en) 1996-09-19 2004-06-29 Usbiomaterials Corp. Anti-inflammatory and antimicrobial uses for bioactive glass compositions
CN1303953C (en) * 1996-09-19 2007-03-14 美国生物材料公司 Composition and method for acceleration of wound and burn healing
US5977204A (en) * 1997-04-11 1999-11-02 Osteobiologics, Inc. Biodegradable implant material comprising bioactive ceramic
US6344496B1 (en) 1997-04-11 2002-02-05 Osteobiologics, Inc. Biodegradable implant material comprising bioactive ceramic
US7524335B2 (en) * 1997-05-30 2009-04-28 Smith & Nephew, Inc. Fiber-reinforced, porous, biodegradable implant device
US20050240281A1 (en) * 1997-05-30 2005-10-27 Slivka Michael A Fiber-reinforced, porous, biodegradable implant device
US6197342B1 (en) 1997-10-01 2001-03-06 Paul D. Thut Use of biologically active glass as a drug delivery system
US6153221A (en) * 1997-10-01 2000-11-28 Paul D. Thut Use of biogically active glass as a drug delivery system
US5972384A (en) * 1997-10-01 1999-10-26 University Of Maryland, Baltimore Use of biologically active glass as a drug delivery system
US6423343B1 (en) 1998-01-23 2002-07-23 Usbiomaterials Corporation Bioactive glass treatment of inflammation in skin conditions
US6517863B1 (en) 1999-01-20 2003-02-11 Usbiomaterials Corporation Compositions and methods for treating nails and adjacent tissues
US6663878B1 (en) 1999-04-29 2003-12-16 Usbiomaterials Corp. Anti-inflammatory bioactive glass particulates
US6482444B1 (en) 1999-06-14 2002-11-19 Imperial College Innovations Silver-containing, sol/gel derived bioglass compositions
US8551508B2 (en) 1999-12-07 2013-10-08 Schott Ag Cosmetic, personal care, cleaning agent, and nutritional supplement compositions and methods of making and using same
US20070275021A1 (en) * 1999-12-07 2007-11-29 Schott Ag New cosmetic, personal care, cleaning agent, and nutritional supplement compositions and methods of making and using same
US6787584B2 (en) 2000-08-11 2004-09-07 Pentron Corporation Dental/medical compositions comprising degradable polymers and methods of manufacture thereof
US20040249015A1 (en) * 2000-08-11 2004-12-09 Weitao Jia Method of manufacturing dental restorations
US20020120033A1 (en) * 2000-08-11 2002-08-29 Weitao Jia Dental/medical compositions comprising degradable polymers and methods of manufacture thereof
US7275933B2 (en) 2000-08-11 2007-10-02 Pentron Clinical Technologies, Llc Method of manufacturing dental restorations
US7732358B2 (en) 2000-09-20 2010-06-08 Goodrich Corporation Inorganic matrix compositions and composites incorporating the matrix composition
US20050022698A1 (en) * 2000-09-20 2005-02-03 Mazany Anthony M. Inorganic matrix compositions and composites incorporating the matrix composition
US20090314181A1 (en) * 2001-01-04 2009-12-24 Primus Carolyn M Dental material
US20040226478A1 (en) * 2001-01-04 2004-11-18 Primus Carolyn M. Dental material
US20050263036A1 (en) * 2001-01-04 2005-12-01 Primus Carolyn M Dental material
US20040086661A1 (en) * 2001-03-16 2004-05-06 Antti Yli-Urpo Sintering of bioactive glass with localised electromagnetic and/or acoustic energy
US20040191292A1 (en) * 2001-06-05 2004-09-30 Laisheng Chou Scaffold product for human bone tissue engineering, methods for its preparation and uses thereof
EP1426066A1 (en) * 2001-06-05 2004-06-09 Yenssen Biotech Co., Ltd. Scaffold product for human bone tissue engineering, methods for its preparation and uses thereof
CN1294885C (en) * 2001-06-05 2007-01-17 江苏阳生生物工程有限公司 Biotechnological body bone tissue rack and its making process and use
EP1426066A4 (en) * 2001-06-05 2006-01-11 Yenssen Biotech Co Ltd Scaffold product for human bone tissue engineering, methods for its preparation and uses thereof
WO2002098474A1 (en) 2001-06-05 2002-12-12 Laisheng Biotechnology Inc., Shanghai Scaffold product for human bone tissue engineering, methods for its preparation ans uses thereof
US9504574B2 (en) 2003-08-22 2016-11-29 Smith & Nephew, Inc. Tissue repair and replacement
US20070129810A1 (en) * 2003-08-22 2007-06-07 Smith & Nephew, Inc. Tissue Repair and Replacement
DE102004021729B4 (en) * 2004-04-30 2017-01-19 Mann + Hummel Gmbh Process for producing a high temperature resistant hollow fiber membrane module
DE102004021729A1 (en) * 2004-04-30 2005-11-24 Mann + Hummel Gmbh Hollow fiber membrane module
US7722246B1 (en) * 2005-04-20 2010-05-25 Carty William M Method for determining the thermal expansion coefficient of ceramic bodies and glazes
US20090208428A1 (en) * 2006-06-16 2009-08-20 Imperial Innovations Limited Bioactive Glass
US9433704B2 (en) 2007-03-09 2016-09-06 Novabone Products, Llc Osteostimulative settable bone graft putty
US20080221701A1 (en) * 2007-03-09 2008-09-11 Jipin Zhong Osteostimulative settable bone graft putty
US20110009511A1 (en) * 2007-07-05 2011-01-13 Imperial Innovations Limited Glass Polycarboxylate Cements
US8357515B2 (en) 2007-12-17 2013-01-22 Queen Mary & Westfield College Latency associated protein construct with aggrecanase sensitive cleavage site
US20100310515A1 (en) * 2007-12-17 2010-12-09 Queen Mary & Westfield College Latency Associated Protein Construct With Aggrecanase Sensitive Cleavage Site
US20110123592A1 (en) * 2008-05-27 2011-05-26 Imperial Innovations Limited Biomaterials
US20110142902A1 (en) * 2008-05-27 2011-06-16 Imperial Innovations Limited Hypoxia Inducing Factor (HIF) Stabilising Glasses
US20110144765A1 (en) * 2008-05-27 2011-06-16 Imperial Innovations Limited Process For Producing Porous Scaffolds From Sinterable Glass
US20120064290A1 (en) * 2008-12-01 2012-03-15 The Furlong Research Charitable Foundation Article and method of surface treatment of an article
US9044528B2 (en) * 2008-12-01 2015-06-02 Ucl Business Plc Article and method of surface treatment of an article
US20100203482A1 (en) * 2009-02-06 2010-08-12 The Trustees Of The University Of Pennsylvania Non-biodegradable endodontic sealant composition
US8614263B2 (en) * 2009-02-06 2013-12-24 The Trustees Of The University Of Pennsylvania Non-biodegradable endodontic sealant composition
US9198842B2 (en) 2009-06-30 2015-12-01 Repregen Limited Multicomponent glasses for use in personal care products
US8795691B2 (en) 2010-03-16 2014-08-05 Brown University Nanotubes and compositions thereof
US10201634B2 (en) 2010-03-16 2019-02-12 Brown University Nanotubes and compositions thereof
US9439766B2 (en) 2012-04-23 2016-09-13 Zimmer, Inc. Multi-layered prosthetic constructs, kits, and methods
WO2016090359A2 (en) 2014-12-05 2016-06-09 Augusta University Research Institute, Inc. Glass composites for tissue augmentation, biomedical and cosmetic applications
US11464740B2 (en) 2019-04-29 2022-10-11 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Method and devices for delivering therapeutics by oral, respiratory, mucosal, transdermal routes

Similar Documents

Publication Publication Date Title
US4103002A (en) Bioglass coated A1203 ceramics
Greenspan et al. Chemical and mechanical behavior of bioglass‐coated alumina
Kitsugi et al. Bone bonding behavior of MgO CaO SiO2 P2O5 CaF2 glass (mother glass of A· W‐glass‐ceramics)
CA1228605A (en) Carbonaceous articles having oxidation prohibitive coatings thereon
Gomez-Vega et al. Bioactive glass coatings with hydroxyapatite and Bioglass® particles on Ti-based implants. 1. Processing
US6171986B1 (en) Bioactive sol-gel compositions and methods
Pazo et al. Silicate glass coatings on Ti-based implants
AU687658B2 (en) Novel bioactive glasses and their use
Hench et al. Bioactive glass coatings
Jiang et al. Coating of hydroxyapatite on highly porous Al2O3 substrate for bone substitutes
GB2080281A (en) Biologically active glass
JPH05270859A (en) Glaze composition and glazing method
US5817326A (en) Processing of hydroxylapatite coatings on titanium alloy bone prostheses
EP0514401A1 (en) Bioactive vitreous composition for bone implants, filaments made therefrom and method
US5705273A (en) Method for strengthening dental restorative materials
Brovarone et al. Graded coatings on ceramic substrates for biomedical applications
Cañas et al. Deposition of bioactive glass coatings based on a novel composition containing strontium and magnesium
GB1581063A (en) Bioglass coated a12o3 ceramics
WO1993017976A1 (en) Bioactive glass as a bone substitute
KR100424910B1 (en) Coating process of bioactive ceramics
DE2703814A1 (en) Dense alumina prosthetic bone implants - coated with biologically active glass
JPS5945384B2 (en) Manufacturing method for high-strength biological components
JPH04250166A (en) Composite implant
Kim et al. On the feasibility of phosphate glass and hydroxyapatite engineered coating on titanium
Peláez et al. Genotoxicity effects of ceramic coatings applied on metallic substrates using single cell gel electrophoresis assay in vitro

Legal Events

Date Code Title Description
AS Assignment

Owner name: UNIVERSITY OF FLORIDA, 207 TIGERT HALL, GAINESVILL

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BOARD OF REGENTS, STATE OF FLORIDA;REEL/FRAME:004391/0113

Effective date: 19820327

AS Assignment

Owner name: WASHINGTON RESOURCES GROUP, INC.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH INC., A CORP. OF DE;REEL/FRAME:005634/0327

Effective date: 19901005

Owner name: REBUILDING SERVICES INC.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH INC., A CORP. OF DE;REEL/FRAME:005634/0327

Effective date: 19901005

Owner name: GRYPHON VENTURES, LIMITED PARTERSHIP

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH INC., A CORP. OF DE;REEL/FRAME:005634/0327

Effective date: 19901005

Owner name: VENTURE FIRST II L.P.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH INC., A CORP. OF DE;REEL/FRAME:005634/0327

Effective date: 19901005

AS Assignment

Owner name: GRYPHON VENTURES I, LIMITED PARTNERSHIP

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC., A CORPORATION OF DE;REEL/FRAME:005758/0025

Effective date: 19910206

Owner name: VENTURE FIRST II L.P.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC., A CORPORATION OF DE;REEL/FRAME:005758/0025

Effective date: 19910206

Owner name: REBUILDING SERVICE, INC.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC., A CORPORATION OF DE;REEL/FRAME:005758/0025

Effective date: 19910206

Owner name: WASHINGTON RESOURCES GROUP, INC.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC., A CORPORATION OF DE;REEL/FRAME:005758/0025

Effective date: 19910206

Owner name: KNELLINGER, RICHARD M.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC., A CORPORATION OF DE;REEL/FRAME:005758/0025

Effective date: 19910206

Owner name: HENCH, LARRY

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC., A CORPORATION OF DE;REEL/FRAME:005758/0025

Effective date: 19910206

AS Assignment

Owner name: WASHINGTON RESOURCES GROUP, INC.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC.;REEL/FRAME:006031/0005

Effective date: 19920214

Owner name: REBUILDING SERVICE, INC.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC.;REEL/FRAME:006031/0005

Effective date: 19920214

Owner name: GRYPHON VENTURES II, LIMITED PARTNERSHIP

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC.;REEL/FRAME:006031/0005

Effective date: 19920214

Owner name: VENTURE FIRST II L.P.

Free format text: SECURITY INTEREST;ASSIGNOR:GELTECH, INC.;REEL/FRAME:006031/0005

Effective date: 19920214